CN109134792B - Cationic phenolic dry strength agent and preparation method thereof - Google Patents

Cationic phenolic dry strength agent and preparation method thereof Download PDF

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CN109134792B
CN109134792B CN201810956801.3A CN201810956801A CN109134792B CN 109134792 B CN109134792 B CN 109134792B CN 201810956801 A CN201810956801 A CN 201810956801A CN 109134792 B CN109134792 B CN 109134792B
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dry strength
strength agent
cationic
preparation
agent
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CN109134792A (en
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施晓旦
马腾
尹东华
金霞朝
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Jining Mingsheng New Material Co ltd
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Jining Mingsheng New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/36—Chemically modified polycondensates by etherifying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/10—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with phenol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Phenolic Resins Or Amino Resins (AREA)
  • Paper (AREA)

Abstract

The invention provides a preparation method of a cationic phenolic aldehyde dry strength agent, which comprises the following steps: step 1, mixing a phenol-containing compound, a formaldehyde monomer, strong base and deionized water, and reacting to obtain a reaction product; and 2, adding a cationic etherifying agent into the reaction product obtained in the step 1, and reacting to obtain the dry strength agent product. The invention also provides the cationic phenolic aldehyde dry strength agent prepared by the preparation method. The cationic phenolic aldehyde dry strength agent is a novel dry strength agent, and can obtain a phenolic aldehyde polymer with a large number of branched chains through the step-by-step polymerization reaction of a plurality of active sites of a phenolic substrate and formaldehyde; and the product has the characteristics of high branched chain and high cationic group through the grafting reaction with the cationic etherifying agent, and the dry strength performance applied to paper is greatly improved.

Description

Cationic phenolic dry strength agent and preparation method thereof
Technical Field
The invention relates to a dry strength agent, in particular to a preparation method of a cationic phenolic dry strength agent.
Background
Dry strength agents are additives to paper making and are used to provide paper with a degree of dry strength, often to compensate for the reduction in paper strength caused by the addition of fillers or low grade fibers (e.g., recycled fibers), by adding dry strength agents to the pulp. The commonly used dry strength agents mainly comprise polyacrylamide and copolymers thereof, including anionic polyacrylamide, cationic polyacrylamide, amphoteric polyacrylamide and the like.
In recent years, the utilization rate of waste paper resources in China is increased year by year, and the development potential is huge. However, the improvement of the utilization rate of the used paper means that the number of times of recycling of the used paper is increased, which causes a large decrease in the paper strength index, so that a more efficient dry strength agent is required to increase the paper strength.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects of the prior art, the preparation method of the cationic phenolic dry strength agent is provided, the dry strength agent with abundant branched chains and cationic groups can be prepared, the application potential is outstanding, and the dry strength performance applied to paper can be greatly improved.
The invention adopts the following technical scheme for solving the technical problems:
one purpose of the invention is to provide a preparation method of a cationic phenolic aldehyde dry strength agent, which comprises the following steps:
step 1, mixing a phenol-containing compound, a formaldehyde monomer, strong base and deionized water, and reacting to obtain a reaction product;
and 2, adding a cationic etherifying agent into the reaction product obtained in the step 1, and reacting to obtain the dry strength agent product.
In order to optimize the above technical solution, the technical measures taken by the present invention further include:
further, the reaction condition in the step 1 is 65-85 ℃, and the reaction time is 120 min; the reaction condition in the step 2 is 50-85 ℃, and the reaction time is 120 min.
Further, the weight percentage of the phenolic compound, the formaldehyde monomer, the strong base and the cationic etherifying agent used for preparing the dry strength agent product is as follows:
Figure BDA0001772858410000021
the balance of deionized water.
Further, the phenol-containing compound is composed of one or more monomers of the compound represented by the general formula (I):
Figure BDA0001772858410000022
wherein, R in the general formula (I)1、R2Is hydrogen, alkoxy or aromatic substituent;
R3is hydrogen, containing C1～C12Saturated or unsaturated alkyl, hydroxyl, carboxyl, carbonyl, sulfonic group, amino or aromatic substituent.
Further, the phenol-containing compound is selected from at least one of phenol, p-hydroxyphenylpropane or guaiacol.
Further, the formaldehyde monomer is at least one selected from paraformaldehyde and formaldehyde.
Further, the strong base is selected from at least one of sodium hydroxide or potassium hydroxide.
Further, the cationic etherifying agent is at least one selected from N- (3-chloro-2-hydroxypropyl) N, N, N trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 2, 3-epoxypropyl trimethyl ammonium chloride.
The invention also aims to provide the cationic phenolic aldehyde dry strength agent prepared by the preparation method.
Further, the solid content of the dry strength agent is 10-50%.
By adopting the technical scheme, compared with the prior art, the invention has the following technical effects:
the cationic phenolic aldehyde dry strength agent is a novel dry strength agent, and can obtain a phenolic aldehyde polymer with a large number of branched chains through the step-by-step polymerization reaction of a plurality of active sites of a phenolic substrate and formaldehyde; and the product has the characteristics of high branched chain and high cationic group through the grafting reaction with the cationic etherifying agent, and the dry strength performance applied to paper is greatly improved.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
The embodiment provides a preparation method of a cationic phenolic aldehyde dry strength agent, which comprises the following steps:
200g of p-hydroxyphenylpropane, 30g of sodium hydroxide (32 wt% of solid content) and 50g of formaldehyde (effective content is 37 wt%) are dissolved in 345g of deionized water, a reaction kettle is heated to 65 ℃ for reaction for 120 minutes, then 50g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added into the reaction kettle for reaction for 120 minutes at 80 ℃, and the reaction kettle is cooled to room temperature to obtain a finished dry strength agent product with the solid content of 40.14%.
Example 2
The embodiment provides a preparation method of a cationic phenolic aldehyde dry strength agent, which comprises the following steps:
300g of guaiacol, 40g of sodium hydroxide (32 wt% of solid content) and 40g of formaldehyde (37 wt% of effective content) are dissolved in 470g of deionized water, a reaction kettle is heated to 75 ℃ to react for 120 minutes, then 40g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added into the reaction kettle to react for 120 minutes at 80 ℃, and the mixture is cooled to room temperature to obtain a finished dry strength agent product with the solid content of 40.52%.
Example 3
The embodiment provides a preparation method of a cationic phenolic aldehyde dry strength agent, which comprises the following steps:
100g of guaiacol, 100g of p-hydroxy-phenyl propane, 20g of sodium hydroxide (32 wt% of solid content) and 20g of formaldehyde (37 wt% of effective content) are dissolved in 550g of deionized water, a reaction kettle is heated to 65 ℃ to react for 120 minutes, then 30g of 2, 3-epoxypropyltrimethylammonium chloride is added into the reaction kettle to react for 120 minutes at 85 ℃, and the reaction kettle is cooled to room temperature to obtain a finished dry strength agent product, wherein the solid content is 30.53%.
Example 4
The embodiment provides a preparation method of a cationic phenolic aldehyde dry strength agent, which comprises the following steps:
dissolving 150g of phenol, 100g of p-hydroxy-phenyl propane, 40g of sodium hydroxide (32 wt% of solid content) and 30g of formaldehyde (37 wt% of effective content) in 1700g of deionized water, heating a reaction kettle to 70 ℃, reacting for 120 minutes, then adding 40g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride into the reaction kettle, reacting for 120 minutes at 60 ℃, and cooling to room temperature to obtain a finished dry strength agent product with the solid content of 19.21%.
Example 5
The embodiment provides a preparation method of a cationic phenolic aldehyde dry strength agent, which comprises the following steps:
200g of guaiacol, 100g of p-hydroxy-phenyl propane, 40g of sodium hydroxide (32 wt% of solid content) and 40g of formaldehyde (effective content is 37 wt%) are dissolved in 470g of deionized water, a reaction kettle is heated to 75 ℃ to react for 120 minutes, then 40g of 3-chloro-2-hydroxypropyl trimethyl ammonium chloride is added into the reaction kettle, and when the reaction kettle is reacted for 120 minutes at 80 ℃, the reaction kettle is cooled to room temperature to obtain a finished dry strength agent, wherein the solid content is 40.31%.
Comparative test
Cationic phenolic dry strength agents prepared by the preparation method of the embodiment 1-5 are respectively used as experimental groups 1-5; a commercial cationic polyacrylamide dry strength agent (solid content is 20%) is used as a control group; a comparison was applied under the same conditions. Wherein the design papermaking quantitative rate is 150g/m2The feeding sequence is as follows: the pulp, aluminum sulfate (3kg/t paper), dry strength agent, CPAM (300ppm) and micro-particle (400ppm), and the addition amount of the dry strength agent is as follows: 7. 12, 18 kg/ton paper (wet/dry; experimental groups 1-5 are each at 20% solids).
The operation is carried out according to the following process:
weighing the pulp, adding a dry strength agent, stirring for 2 minutes, adding CPAM and the microparticles, stirring for 2 minutes respectively, papermaking by using a LABTECH73-62 semi-automatic sheet former and squeezing by using a LABTECH 73-50 standard sheet squeezer, drying and balancing, and then detecting the quantification, folding endurance and bursting endurance of the paper.
The detection results are shown in table 1:
table 1 comparison of dry strength agent effect for each group
Figure BDA0001772858410000041
Figure BDA0001772858410000051
As can be seen from the above table, when the dry strength agent prepared by the preparation method of the present invention is applied to paper, the bursting strength and the folding strength of the paper can be significantly improved with a small amount of the dry strength agent added compared to the control group.
The embodiment shows that the preparation method of the cationic phenolic aldehyde dry strength agent can prepare the dry strength agent with rich branched chains and cationic groups by carrying out polymerization and cationization modification on ortho-para positions of benzene rings in a phenol-containing substrate, has outstanding application potential, and can greatly improve the dry strength performance applied to paper.
The embodiments of the present invention have been described in detail, but the embodiments are merely examples, and the present invention is not limited to the embodiments described above. Any equivalent modifications or alterations to this practice will occur to those skilled in the art and are intended to be within the scope of this invention. Accordingly, equivalent changes and modifications made without departing from the spirit and scope of the present invention should be covered by the present invention.

Claims (3)

1. A preparation method of a cationic phenolic aldehyde dry strength agent is characterized by comprising the following steps:
step 1, mixing a phenol-containing compound, a formaldehyde monomer, strong base and deionized water, and reacting to obtain a reaction product;
step 2, adding a cationic etherifying agent into the reaction product obtained in the step 1, and reacting to obtain a dry strength agent product;
the reaction condition in the step 1 is 65-85 ℃, and the reaction time is 120 min; the reaction condition in the step 2 is 50-85 ℃, and the reaction time is 120 min;
the weight percentage of the phenolic compound, the formaldehyde monomer, the strong base and the cationic etherifying agent used for preparing the dry strength agent product is as follows:
Figure FDA0002970634410000011
the balance of deionized water;
the phenol-containing compound is selected from at least one of phenol, p-hydroxyphenylpropane or guaiacol; the formaldehyde monomer is at least one of paraformaldehyde or formaldehyde; the strong base is selected from at least one of sodium hydroxide or potassium hydroxide; the cationic etherifying agent is at least one selected from N- (3-chloro-2-hydroxypropyl) N, N, N trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride and 2, 3-epoxypropyl trimethyl ammonium chloride.
2. The cationic phenolic dry strength agent prepared by the preparation method of claim 1.
3. The dry strength agent according to claim 2, wherein the solid content of the dry strength agent is 10% to 50%.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2259503A (en) * 1937-07-13 1941-10-21 Wassenegger Hans Etherified cation exchanging phenol-formaldehyde resins
US4310653A (en) * 1980-10-08 1982-01-12 Desoto, Inc. Production of monomeric etherified bisphenol-formaldehyde condensates
JPS59215309A (en) * 1983-05-23 1984-12-05 Unitika Ltd Phenolic resin having ion exchange group, its production and adsorption treatment therewith
US6048438A (en) * 1995-11-08 2000-04-11 Nalco Chemical Company Method to enhance the performance of polymers and copolymers of acrylamide as flocculants and retention aids
CN101050611A (en) * 2007-05-14 2007-10-10 南京林业大学 Surface sizing agent for improving paper deflection and paperboard circular press stength
CN102604322A (en) * 2012-02-15 2012-07-25 山东圣泉化工股份有限公司 Phenolic resin compound for wet-curtain paper, preparation method of phenolic resin compound and preparation method of wet-curtain paper
CN104674601A (en) * 2015-02-02 2015-06-03 天津市浩宇助剂有限公司 Macromolecular papermaking dry strength agent

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2259503A (en) * 1937-07-13 1941-10-21 Wassenegger Hans Etherified cation exchanging phenol-formaldehyde resins
US4310653A (en) * 1980-10-08 1982-01-12 Desoto, Inc. Production of monomeric etherified bisphenol-formaldehyde condensates
JPS59215309A (en) * 1983-05-23 1984-12-05 Unitika Ltd Phenolic resin having ion exchange group, its production and adsorption treatment therewith
US6048438A (en) * 1995-11-08 2000-04-11 Nalco Chemical Company Method to enhance the performance of polymers and copolymers of acrylamide as flocculants and retention aids
CN101050611A (en) * 2007-05-14 2007-10-10 南京林业大学 Surface sizing agent for improving paper deflection and paperboard circular press stength
CN102604322A (en) * 2012-02-15 2012-07-25 山东圣泉化工股份有限公司 Phenolic resin compound for wet-curtain paper, preparation method of phenolic resin compound and preparation method of wet-curtain paper
CN104674601A (en) * 2015-02-02 2015-06-03 天津市浩宇助剂有限公司 Macromolecular papermaking dry strength agent

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Denomination of invention: A cationic phenolic dry strength agent and its preparation method

Effective date of registration: 20220623

Granted publication date: 20210615

Pledgee: Jining Yanzhou sub branch of Rizhao Bank Co.,Ltd.

Pledgor: JINING MINGSHENG NEW MATERIAL Co.,Ltd.

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